Process for the purification of a cryogenic fluid by filtration and/or adsorption

ABSTRACT

Process and apparatus for the purification of a cryogenic fluid in liquid, diphase, gaseous or supercritical state, having boiling point Pe, with at least one of its impurities having a boiling point Pe&#39;, with Pe&#39;&gt;Pe. The process includes at least one step selected from the group comprised by: 
     a filtration step of at least one impurity in solid state, 
     and an adsorption step of at least one impurity in liquid or gaseous state; 
     and in which there is recovered at least one portion of the cryogenic fluid at least partially purified.

This application is a division of copending application Ser. No.08/790,362, filed Jan. 28, 1997.

FIELD OF THE INVENTION

The present invention relates to the field of purification of cryogenicfluids and, more particularly, to a process and a device for thepurification of a cryogenic fluid in liquid, gaseous, supercritical ordiphase state with at least one of the impurities in a solid and/orliquid and/or gaseous state which it contains.

BACKGROUND OF THE INVENTION

At present, cryogenic fluids find use in numerous and various fields ofindustry. Thus, nitrogen, helium, neon, argon, deuterium, krypton, andxenon are at present used in the electronic field.

This field especially requires these compounds to be as pure aspossible, which is to say stripped of most of their impurities, so as toavoid subsequent degradation of the electronic components by reactionwith said impurities. By way of example, can be cited the use of ultrapure helium, as inert gas utilizable in constant temperature control ofthe support chips for integrated circuits forming memories orprocessors, or in the cooling of "wafers".

There is also an increase in demand in the electronic field as to thesupply of ultra pure hydrogen.

Numerous processes for purification of cryogenic fluids, such as inertfluids, are known from the prior art, but these latter generally haveseveral drawbacks or disadvantages, namely:

they are not suitable for purification of cryogenic fluids no matterwhat their state, namely liquid, gas, supercritical and/or diphase, andtherefore require heating and/or cooling steps, as the case may be, tobring the cryogenic fluid to be purified to a given temperature, atwhich the elimination of the impurities can be carried out;

they require the use of costly adsorbents, for example of the gettertype;

the adsorbents used are not effective unless "hot", that is, attemperatures higher than 0° C., even at 100° C.;

they are limited as to the quantity of cryogenic fluid that can betreated during a given period of time;

they are limited to one type of cryogenic fluid, for example argon orhelium, which is to say that the same process and/or the same devicecannot be used to purify cryogenic fluids of different types;

they are limited as to the impurities that can be eliminated by the useof adsorbents or catalysts which react only in a selective manner, whichis to say with certain impurities and not others, with the result that acryogenic fluid is only partially purified; for example, theconventional adsorbents or catalysts do not permit eliminating nitrogenimpurities contained in helium.

they generally comprise one or several oxidative catalytic steps so asto convert particularly the hydrogen and/or carbon monoxide impuritiesinto water and/or carbon dioxide.

Thus, U.S. Pat. No. 3,996,082 discloses a process for the purificationof gaseous argon from its oxygen impurity by means of a syntheticzeolite of type A.

U.S. Pat. No. 2,874,030 discloses itself a process for the purificationof gaseous argon from its oxygen impurity, in which the oxygen istransformed into water by catalytic reaction with excess hydrogen; thewater formed being then eliminated by dehydration.

EP-A-0 350 656 discloses moreover a process for the purification of aninert gas of its oxygen, carbon monoxide and hydrogen impurities, inwhich the carbon monoxide and the hydrogen are eliminated by catalyticoxidation at a temperature comprised between 150° C. and 250° C. in thepresence of a first reduced copper-based catalyst, then a secondoxidized copper-based catalyst, giving carbon dioxide and water, whichare then eliminated by adsorption at ambient temperature on an adsorbentof the molecular sieve type.

Moreover, FR 9604955 discloses a process to supply a utilization conduitwith ultra pure helium, in which helium is withdrawn in liquid phase orin supercritical phase from a storage reservoir, the helium is filteredby means of a steel cloth so as to retain solid impurities, the filteredhelium is vaporized and is sent to the utilization conduit. It isrecited in this document that the hydrogen and/or neon impuritiesdissolved in the liquid or supercritical helium are not retained.

FR 9507943 discloses itself a process of purification of inert gases,such as nitrogen and rare gases, of their oxygen and carbon monoxideimpurities, by adsorption at a temperature below 30° C. on a specificadsorbent of the porous metallic oxide type; the hydrogen impurity isthen eliminated by distillation.

Moreover, FR 9611271 relates to the purification of a cryogenic fluid,such as liquid nitrogen, liquid argon or liquid helium, of its hydrogen,carbon monoxide and/or oxygen impurities, by adsorption on a support ofthe type of alumina, silica, zeolite or titanium oxides supporting ametal, such as platinum, palladium, rhodium or iridium.

Moreover, U.S. Pat. No. 4,659,351 discloses a process in two steps forobtaining liquid helium, in which a gaseous flow consisting essentiallyof helium and nitrogen with several minor impurities is subjected to acooling step so as to condense said minor impurities and nitrogen, whichare then eliminated; the gaseous flow enriched in helium is thensubjected to a PSA type process (pressure swing adsorption) or a processof adsorption by pressure variation, from which results a flow ofrelatively pure gaseous helium, which helium is then condensed to liquidhelium. It will be easily understood that this process has numerousdisadvantages and drawbacks, not only as to the cost of energy but alsoas to the purity of helium obtained. Thus, the requirement to use thesteps of vaporization/liquefaction of helium is very costly from a pointof view of energy and finance, and although the helium obtained will berelatively pure, it contains quantities of impurities too high to beused particularly for electronics.

SUMMARY OF THE INVENTION

The object of the present invention is therefore to provide a processand a device for the purification of cryogenic fluids no matter whattheir state, namely liquid, diphase, gaseous or supercritical, whichwill be less costly from the economic and energy standpoint than theprocesses and devices existing at present, which is suitable for thepurification of different cryogenic fluids, which permits obtaining purecryogenic fluids, which is to say free from at least their principalsolid and/or liquid and/or gaseous impurities.

The invention thus relates to a process for the purification of acryogenic fluid in liquid, diphase, gaseous or supercritical state,having a boiling point Pe, of at least one of its impurities having aboiling point Pe', with Pe'>Pe, comprising at least one purificationstep selected from the group comprised by:

a step of mechanical filtration of at least one impurity in solid state,

and a step of adsorption of at least one impurity in liquid or gaseousstate,

and in which there is recovered at least a portion of the cryogenicfluid at least partially purified.

In other words, the impurities in solid state (crystalline) contained inthe cryogenic fluid to be purified are retained by mechanicalfiltration, whilst the impurities in liquid or in gaseous phase areadsorbed by means of at least one adsorbent material.

As the case may be, the process of the invention could comprise moreoverone or several of the following characteristics:

the cryogenic fluid is such that its boiling point Pe is less than -100°C., preferably less than -150° C., more preferably below -240° C. (at apressure of 10⁵ Pa);

the cryogenic fluid to be purified is selected from the group comprisedby helium, hydrogen, deuterium (D₂), krypton, xenon, neon and argon(there is understood by helium: helium and its isotopes He³ and He⁴);

the cryogenic fluid to be purified is helium and the eliminatedimpurities are from the group comprised by hydrogen, neon, nitrogen,carbon monoxide, carbon dioxide, oxygen, argon, xenon, krypton,hydrocarbons and water;

the cryogenic fluid to be purified is hydrogen and the impurities arefrom the group comprised by neon, nitrogen, carbon monoxide, carbondioxide, oxygen, argon, xenon, krypton, hydrocarbons and water;

the cryogenic fluid to be purified is neon and the impurities are fromthe group comprised by nitrogen, carbon monoxide, carbon dioxide,oxygen, argon, xenon, krypton, hydrocarbons and water;

the mechanical filtration carried out by means of a metal or ceramicfilter, or by means of adsorbent material used to eliminate impuritiesin the liquid or gaseous state. Thus, said adsorbent material can alsoserve as a filter so as to retain the particles and solid impurities(crystalline) contained in the cryogenic fluid to be purified; in thiscase, the steps of filtration and adsorption will be simultaneous.

the adsorption of the impurities is carried out by means of an adsorbentchosen from the group comprised by active carbon, zeolites, silica gelor any other porous adsorbent permitting retaining effectively one orseveral types of soluble or gaseous impurities in the cryogenic fluid tobe purified, for example, a carbon cloth.

at least one mechanical filtration step is carried out upstream and/ordownstream of at least one adsorption step and, preferably, upstream anddownstream of the adsorption step. It is also possible to alternateseveral adsorption steps and several steps of filtration by usingidentical adsorption materials and filtration means, analogous ordifferent in the different steps.

the adsorbent used in the adsorption step of the impurities contained inthe cryogenic fluid is subjected to at least one step of regeneration.This regeneration of the adsorbent material can be carried out forexample by the following operative procedure:

stoving for several hours at a temperature of 100° C. to 150° C. of theadsorbent material, such as active carbon (only during the first use ofthe adsorbent material);

sweeping or purging the purifier with the help of an inert gas such asnitrogen, at ambient temperature and at atmospheric pressure;

and subsequently sweeping with the aid of the gas to be purified atambient temperature and at atmospheric pressure.

After this double sweeping, the purification system is adapted to carryout a new purification phase.

The invention also relates to a device for practicing the processaccording to the invention, characterized in that it comprises apurifying zone of the cryogenic fluid to be purified, which purifyingzone comprises at least one mechanical filter and/or at least oneadsorbent bed, supply means for the cryogenic fluids to be purified tosaid purification zone, and means for recovering purified cryogenicfluid.

As the case may be, the device of the invention can also comprise:

storage means for the purified cryogenic fluid;

conduit means for bringing the purified cryogenic fluid to a utilizationsite;

means for regenerating the adsorbent material, permitting regenerationof said adsorbent material, for example according to the operativecondition mentioned above.

The process of the invention can thus preferably be used to purify acryogenic liquid, which will be in the state:

liquid or cooled, which is to say at a temperature below its boilingpoint,

gaseous, which is to say at a temperature higher by several degrees thanits liquefaction temperature or boiling point, for example being at atemperature between 5° C. and 20° C. above its boiling point.

diphasic, which is to say in the form of a liquid/gas mixture, hence ata temperature substantially equal to the boiling point, or fluctuatingabout said boiling point,

or supercritical, for example in the case of helium, at a temperature ofabout -268° C. for a pressure of 2,275.10⁵ Pa.

The advantage of the invention resides in the fact that it permits ultrapurification of the cryogenic fluids having a boiling temperature, atatmospheric pressure, below -100° C., preferably below -150° C., morepreferably below -240° C., such as helium, krypton, xenon, argon,hydrogen, deuterium (D₂), or neon, from at least one of their impuritieshaving a boiling point higher than that of said cryogenic fluid, whetherin the solid and/or liquid and/or gaseous state, by means of mechanicalfiltration steps and/or adsorption of said impurities.

The process of the invention will preferably be practiced over atemperature range comprised between about -273° C. and -240° C., and fora pressure range comprised between 10⁵ Pa and 30.10⁵ Pa, preferablybetween 10⁵ Pa and 10.10⁵ Pa.

By way of example, the boiling points or temperatures, at atmosphericpressure, of different compounds are given in Table 1 as follows:

                  TABLE 1                                                         ______________________________________                                               Compound                                                                              Pe (°C.)                                                ______________________________________                                               Argon   -185.80                                                               Nitrogen                                                                              -195.60                                                               Xenon   -108.10                                                               Krypton -153.35                                                               Neon    -246.05                                                               Oxygen  -182.97                                                               Helium  -268.90                                                               Hydrogen                                                                              -252.77                                                               Methane -161.52                                                               Propane -42.04                                                                Ethane  -88.68                                                                CO.sub.2                                                                              -78.50                                                                NO      -151.75                                                               CF.sub.4                                                                              -127.94                                                               D.sub.2 -249.58                                                        ______________________________________                                    

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will now be described in more detail with the helpof examples given by way of illustration, but not limiting theinvention, with reference to the accompanying drawings.

FIG. 1 shows a conventional experimental device which can be used tocarry out the tests recited hereafter.

FIG. 2 shows an industrial device for practicing the process accordingto the invention.

DETAILED DESCRIPTION OF THE INVENTION

In FIG. 1 is shown a vacuum insulated reservoir 1 so as to avoid orminimize any entry of heat, containing liquid helium 2 and a helium sky3. In this experimental device, the purification zone for heliumpolluted by impurities is constituted by a cartridge 4 containing anadsorbent material, here active carbon, adapted to adsorb the impuritiesof the liquid or gas type and two mechanical filters 5 and 5', providedrespectively upstream and downstream of said purification cartridge 4,said filters 5, 5' being adapted to stop the impurities of solid type(crystalline).

A mechanical filter is conventionally provided by compression of ametallic powder, such as a powder of a metal or metal alloy, preferablystainless, and embodied as a disc of the compacted structure obtained.It is possible to vary the geometry of the disc or filter obtained byacting particularly on its diameter, its thickness and its porosity. Byway of example, can be cited filters or metallic sinters sold by thecompany PORAL or by the company METAFRAN. Certain sealing joints canalso be provided for such a metallic mechanical filter, for example thejoint VCR (surface sealed connections for metallic joints) produced bythe CAJON company.

Liquid polluted helium 2 enters the purification zone in the directionindicated by arrow 6, which is to say from bottom to top. The solidimpurities are all first stopped by the filter 5, then the liquidimpurities are adsorbed in the purification cartridge 4 by the adsorbentmaterial, for example active carbon, and to finish, the solid particleswhich can be generated by attrition of the adsorbent material arestopped by the filter 5'.

The ultra pure liquid helium thus obtained is brought via the conduit 7to the analyzers 9 and 9' or, as the case may be, discharged to the airat 8.

According to this arrangement, purification is effected of helium inliquid phase. However, to test the efficacy of the process of theinvention on gaseous helium, the same process is conducted but by usingthis time the purification region in the gaseous sky 3 such that theinlet opening 10 for helium in the filter 5 is located above the levelof the liquid helium, hence in the gaseous sky, from which is thusremoved gaseous helium to be purified.

In all cases, bringing the gaseous or liquid helium through successivelythe filter 5, the purification cartridge 4, the filter 5' and thepassage 7 is effected in a conventional manner, by increasing thepressure exerted in the receptacle 1.

This experimental system is connected via conduits 7 and 7' to areservoir 12 containing ultra pure helium permitting purging, which isto say cleaning, the purification zone comprising the filters 5 and 5'and the purification cartridge 4, in particular prior to or after apurification step.

Moreover, another reservoir 11 contains, itself, a helium polluted byknown quantities of impurities adapted to pollute artificially theliquid or gaseous helium contained in the receptacle 1 with knownquantities of pollutants and, in this way, to test the effectiveness ofthe purification process of the invention.

In FIG. 2 is shown an industrial purification device for liquid helium.Liquid helium 22 surmounted by a gaseous helium sky 23 is contained inan insulated reservoir 21, for example a storage reservoir or the tankof a truck.

Gaseous helium 23 or liquid helium 22 is withdrawn from the insulatedreservoir 21 via withdrawal means 23' or 22', respectively, and brought,via a conduit 27', to a purification zone comprising a first filter 25,located upstream of a purification cartridge 24 containing an adsorbentmaterial, such as active carbon or any other suitable porous adsorbentmaterial permitting adsorbing one or several impurities in liquid orgaseous phase, which purification cartridge 24 is located upstream of asecond filter 25'.

Polluted helium from the reservoir 21 is thus purified in thepurification zone and the ultra pure helium obtained is brought, via theconduit 27, to an insulated reservoir 30 for ultra pure helium or, asthe case may be, to a utilization site (not shown).

It will be easily understood that the handling of the cryogenic fluidsis a delicate operation and that, to ensure optimum purification, it isnecessary to be careful that the assembly of the device using thepresent invention be correctly insulated, so as to avoid, or even toeliminate, any entry of troublesome heat; vacuum insulation ispreferred.

Moreover, as will be seen in the following illustrative examples, onecould also, as the case may be, pass from one to the other, namely thetwo filters 25 and 25' and obtain nevertheless an ultra pure cryogenicfluid responding to the desired requirements, particularly to therequirements in the electrical field. In this case, it is the porousadsorbent material which ensures both the mechanical filtration of thesolid particles and the adsorption of the impurities in liquid orgaseous state.

So as to permit the regeneration of the adsorbent material located inthe purification cartridge and the filters which retain the solidimpurities, it is necessary or desirable to subject the purificationzone to a regeneration process, for example a conventional process usinga return of the purification zone to ambient temperature by means ofsweeping said purification zone with an inert gas, such as nitrogen, soas to sublime and/or desorb the adsorbed and/or retained pollutants,followed by a cleansing, which is to say a sweeping, with first ultrapure gaseous helium, then ultra pure liquid helium, before any newpurification phase.

EXAMPLES

In the following examples, the quantities of impurities present in thecryogenic fluid to be purified are determined with the aid of analyzersnow on the market. Thus, the quantities of carbon monoxide and hydrogenimpurity are measured by means of an RGA3 chromatograph sold by TRACEANALYTICAL company, whose detection level is of the order of 1 ppb forcarbon monoxide and 5 ppb for hydrogen (ppb=part per billion by volume),and the quantity of oxygen impurity is measured by means of an analyzerof the OSK type sold by the company OSAKA SANSO KOGYO, which has adetection level of: 1 ppb for oxygen.

For a more exhaustive analytical procedure, the other impurities(nitrogen, neon, carbon dioxide . . . ) can be easily detected by meansof suitable analyzers, such as an analyzer of the APIMS (AtmosphericPressure Ion Mass Spectrometry) type whose detection level for theseimpurities is below 1 ppb.

A conventional device that can carry out the different tests is shown inFIG. 1.

Example 1

In this example, the purification of liquid hydrogen from its impuritiesO₂, CO and H₂ has been carried out solely by mechanical filtration bymeans of a sintered body, comprised of a VCR joint provided with aporous metallic filter (thickness 2.5 mm, porosity 2 μm) sold by theSWAGELOCK company.

At the temperature of liquid helium, the impurities other than hydrogenare in solid form, whilst a fraction of the hydrogen is still in liquidphase.

Before purification, the liquid helium contains about 1 ppm (part permillion by volume) of carbon monoxide, about 5 ppm oxygen and about 2ppm hydrogen, and other solid impurities in the form of traces, namelycarbon dioxide, water, nitrogen and neon.

After purification, the purified helium contains less than 1 ppb ofcarbon monoxide and less than 1 ppb oxygen; by contrast, a residue offrom 100 ppb to several hundreds ppb hydrogen is detected downstream ofthe filter (as a function of the operative conditions of pressure andtemperature).

The purification of the liquid helium on a mechanical filter thus hasits limits as to the hydrogen impurity. Nevertheless, such a filtrationis sufficient when the helium to be purified contains no impurities ofthe hydrogen type, given that all the other impurities are stopped.

Example 2

This example is in all ways analogous to the preceding example exceptthat the mechanical filtration (filter or metallic sinter) is associatedwith an adsorption, particularly hydrogen on a suitable adsorbent, hereactive carbon.

In this case, the use of mechanical filtration coupled with adsorptionpermits obtaining ultra pure liquid helium, no longer containing thistime, contrary to the preceding example, impurities of the hydrogentype. Thus, this hydrogen impurity is adsorbed by the active carbon.

The ultra pure helium thus obtained all together meets the requirementsand necessities of use for electronic purposes, which is to say that thepurified liquid helium contains less than 1 ppb of these variousimpurities.

It is to be noted that the adsorption of the impurities soluble inliquid helium, for example hydrogen, can be carried out upstream and/ordownstream of the mechanical filtration. Preferably, mechanical filtersare disposed on opposite sides of the adsorbent material.

Example 3

This example is like the preceding examples except that the eliminationof the impurities contained in the liquid helium is effected only bymeans of a bed of particles of an adsorbent material, here again a bedof active carbon; in other words, the metallic mechanical filters havebeen omitted.

In a surprising way, there is obtained, as in Example 2, ultra pureliquid helium and this despite the omission of the mechanical filters.The microporous active carbon therefore permits not only adsorbingliquid or gaseous impurities, but also filtering, which is to sayretaining mechanically, the solid or crystallized impurities (adsorptionand filtration taking place simultaneously).

Example 4

This example is like Example 2, except that the helium to be purifiedcontains not only carbon monoxide, hydrogen and oxygen impurities, butalso other impurities, namely: water, carbon dioxide (1 ppm), nitrogen(1 ppm) and neon (1 ppm).

The liquid helium after purification contains, here also, less than 1ppb of its different pollutants and the impurities H₂ O, CO₂, N₂ and Neare totally eliminated.

Example 5

This example is like Example 2, except that the adsorbent (activecarbon) is replaced by a carbonized cloth, for example of the typeActitex CS 1501 sold by the ACTITEX company.

The results obtained are identical to those of Example 2.

Here again, there is obtained an ultra purification of the liquid heliumwhen mechanical filtration and adsorption by the carbonated cloth arecombined.

Example 6

This example is like Example 2, except that the cryogenic fluid to bepurified is neon (Te=-246° C.) in liquid phase, which is polluted withthe following impurities having higher boiling points than that of neon:nitrogen (4 ppm), oxygen (1 ppm), carbon dioxide (2 ppm) and ethane (1ppm).

After purification, the ultra pure neon obtained contains undetectablequantities of these different impurities (relative to the analyzersused).

The process of the invention is thus applicable to the purification ofneon.

Example 7

This example is identical to Example 2, except that the cryogenic fluidto be purified is krypton (Te=-153° C.,) in liquid phase, which ispolluted with the following impurities having boiling points higher thanthat of krypton: water (3 ppm), ethane (2 ppm) and carbon dioxide (2ppm).

After purification, the ultra pure krypton obtained, containsundetectable quantities of these various impurities.

The process of the invention is hence applicable to the purification ofkrypton.

Example 8

This example is identical to Example 2, except that the cryogenic fluidto be purified is xenon (Te=-108° C.) in liquid phase, which is pollutedwith the following impurities having boiling points higher than that ofxenon: water (3 ppm), CO₂ (2 ppm), ethane (1 ppm).

After purification, the ultra pure xenon obtained contains undetectablequantities of these various impurities.

The process of the invention is hence applicable to the purification ofxenon.

We claim:
 1. Process for the purification of hydrogen or deuterium inliquid, diphasic, gaseous or supercritical phase by removal of itscarbon dioxide and water impurities, and at least one other of itsimpurities selected from the group consisting of neon, nitrogen, carbonmonoxide, oxygen, argon, krypton, xenon, and hydrocarbons, the processcomprising the steps of:filtering at least one impurity in solid state;adsorbing at least one impurity in liquid or gaseous state; andrecovering at least a portion of purified hydrogen or deuterium, saidpurified hydrogen or deuterium containing no more than 1 ppb of saidimpurities.
 2. Process according to claim 1, wherein the filtering stepis carried out by passing hydrogen or deuterium through one of a metalor ceramic filter or an adsorbent material.
 3. Process according toclaim 1, wherein the adsorption step is carried out on an adsorbentmaterial selected from the group consisting of active carbon, carbonizedcloth, zeolites, silica gel, and mixtures thereof.
 4. Process accordingto claim 1, further comprising at least one mechanical filtration stepcarried out upstream and/or downstream of the adsorption step. 5.Process according to claim 1, wherein the purification of hydrogen ordeuterium is carried out at a pressure ranging between 1×10⁵ Pa and30×10⁵ Pa.
 6. Process according to claim 5, wherein the purification ofhydrogen or deuterium is carried out at a pressure ranging between 1×10⁵Pa and 10×10⁵ Pa.
 7. Process according to claim 3, wherein the adsorbentused in the adsorption step of the impurities contained in hydrogen ordeuterium is subjected to a regeneration step.
 8. Apparatus for thepurification of hydrogen or deuterium in liquid, diphasic, gaseous orsupercritical phase by removal of its carbon dioxide and waterimpurities, and at least one other of its impurities selected from thegroup consisting of neon, nitrogen, carbon monoxide, oxygen, argon,krypton, xenon, and hydrocarbons, the apparatus comprising:a source ofpolluted hydrogen or deuterium; a purification zone fluidly connected tosaid source of polluted hydrogen or deuterium; said purification zonecomprising at least one mechanical filter and at least one adsorbentbed; and recovery means fluidly connected to said purification zone forrecovering at least a portion of purified hydrogen or deuteriumcontaining no more than 1 ppb of said impurities from said purificationzone.
 9. Apparatus according to claim 8, further comprising storagemeans for storing purified hydrogen or deuterium.
 10. Apparatusaccording to claim 8, further comprising conduit means for conveyingpurified hydrogen or deuterium toward a utilization site.
 11. Apparatusaccording to claim 8, further comprising means for regenerating theadsorbent bed.